Ethoxylated aliphatic tertiary amines to reduce ozone attack on dyes in polyamide fibers

ABSTRACT

WHERE R is an alkyl or aralkyl radical having seven to 24 carbon atoms, R can contain one or two oxygen atoms as ester or ether linkages, R&#39;&#39; is alkylene, and has from two to ten carbons, and x, y and z are each at least 1 and total 10, or preferably 3, are coated on nylon fiber or added to nylon polymer before spinning, improved dyefastness is achieved when the fiber is exposed to ozone.   WHERE R is an alkyl or aralkyl radical having seven to 24 carbon atoms, R can contain one or two oxygen atoms as ester or ether linkages, and x and y are integers such that x and y are each at least 1, and x + y is not more than 10, preferably 2, or ditertiary amines such as   When from about 0.1 percent to about 8 percent of tertiary amines such as:

United States Patent [191 Lofquist et al,

[4 Jan.7,1975

[ ETHOXYLATED ALIPHATIC TERTIARY AMINES TO REDUCE OZONE ATTACK ON DYES IN POLYAMIDE FIBERS [75] Inventors: Robert Alden Lolquist; Peter Reginald Saunders; Richard Eugene Mayer, all of Richmond, Va.

[73] Assignee: Allied Chemical Corporation, New

York, N.Y.

22 Filed: Apr. 3, 1972 [21] App]. No.: 240,812

Related U.S. Application Data [63] Continuation-impart of Ser. No. 165,352, July 22,

1971, abandoned.

OTHER PUBLICATIONS Exparte Weisbein et a1., Patent File No. 3,679,351, 8 pages, Paper No. 18, Appeal No. 97042. Salvin, American Dyestuff Reporter, Pages 12-20 TP890A512.

A, RCH N Primary Examiner-Donald Levy Attorney, Agent, or FirmRichard A. Anderson [57] ABSTRACT When from about 0.1 percent to about 8 percent of tertiary amines such as:

HCHO H (C HCHO a 2 y where R is an alkyl or aralkyl radical having seven to 24 carbon atoms, R can contain one or two oxygen atoms as ester or ether linkages, and x and y are integers such that x and y are each at least 1, and x y is not more than 10, preferably 2, or ditertiary amines such as CH CH O H 2 2 x B. R"---- N (CH CH O) H RCH N(CH CH O) H where R is an alkyl or aralkyl radical having seven to 24 carbon atoms, R can contain one or two oxygen atoms as ester or ether linkages, R is alkylene, and has from two to ten carbons, and x, y and z are each at least 1 and total 10, or preferably 3, are coated on nylon fiber or added to nylon polymer before spinning, improved dyefastness is achieved when the fiber is exposed to ozone.

10 Claims, No Drawings CROSS REFERENCE TO RELATED APPLICATION ETHOXYLATED ALIPHATIC TERTIARY AMINES Basic anthraquinone dyes, such as CT. Basic Blue 47, TO REDUCE OZONE ATTACK ON DYES IN are also subject to ozone fading as shown in Examples POLYAMIDE FIBERS II to XVII. Typical anthraquinone dyes are shown by 'l i US. Pat. No. 2,900,216. Analysis of C.I. Basic Blue 47 or Astrazon Blue 3RL has shown it is quaternized from the compound labeled 2 in the list of compounds on page 1 of US. Pat. No. 2,900,216. Thus, the structure This application is a continuation-in-part application per hundred million. Despite this extremely low conwith carbon-carbon double bonds.

Jla tbss lus r of copending application Ser. No. l6 Ju l y would be:

It I O NH -CH N (CH 3 (D A 9 where A is an anion,

22, 1971 and now abandoned, by Robert A." Eofquist, such as C] 'e' The 1963 Supplement of the Colour Peter R. Saunders, and Richard E. Mayer. Index also indicates Astrazon Blue 3 RL is an anthra- BACKGROUND OF THE INVENTION qumone- The dye diffuses through the fiber to contact the The object of this invention is to reduce or prevent ozone at the surface of the fiber. Part of the evidence the fading of dyed nylon fabrics caused by ozone. By for this is that any treament or additive that increases fading is meant loss of fastness of the dye, i.e., the dye the mobility of the dye, increases its ozone fading. becomes less gh of Changes P e, There is some evidence that water is necessary to blue to light blue.

give ozone fading, but whether its action is that it swells Ozone is present in air at sea level at a concentration the nylon or is involved in a primary or secondary oxiof only I to 5 parts per hundred million. Only under dation step is unclear. conditions of heavy Smog does it rise as high as 60 Parts Ozone fading can be decreased by reduction of the specific surface area of the yarn. This is undesirable when a bulky yarn is required. Ozone fading can also be decreased by changes in polymer morphology and orientation but these techniques are inherently expensive.

centration of ozone, severe fading is observed.

Ozone is an allotropic form of oxygen. The molecule of ozone consists of three atoms of oxygen whereas a molecule of oxygen contains two atoms of oxygen. Ozone is formed in the upper atmosphere by the action of high energy radiation from the sun splitting oxygen molecules into two oxygen atoms. These atoms then combine with oxygen (0 molecules to form ozone 40 (O This ozone then diffuses down through the atmosphere.

Ozone is an electrophilic reagent, that is, it searches out and attacks electron pairs such as those existing SUMMARY OF THE INVENTION A method and composition have been found for improving fastness of dyes when exposed to ozone in poly carbonamide fibers. The method is exposing the fibers to ozone in the presence of a compound selected from the group consisting of tertiary amines and ditertiary amines of the formula H O H (CH2CH2O)xH (CHZC 2 )x A. RCH2N\ and B. R""-N\ CH CH O H CH CH 0 H 2 2 y l 2 2 y RCHZN (CHZCHZO) ZH The dyes which are attacked are usually anthraquiwhere R is an alkyl or aralkyl radical having seven to none type disperse dyes, although it is believed that 24 carbon atoms, R can contain one or two oxygen under severe conditions almost all dyes might be afatoms as ester or ether linkages, R'is a straight chain fected by ozone. alkyl radical having two to ten carbon atoms, and x, y,

One of the most sensitive dyes to ozone fading is disd Z are h t l st 1 nd x, y and 2 total not m perse blue 3- The major consitufi 0f disp se Blue 3 than 15. One of these compounds or mixtures of them can be coated on nylon fiber in amounts of from about 0.1 to about 8 percent, preferably from about 0.1 to about 5 percent on the weight of the fiber. Alternatively, a composition can be prepared from a nylon polymer containing from about 0.1 to 8 percent by weight of the same tertiary amines. The rate of fading of the dye in nylon fibers, particularly disperse or cationic dyes, is substantially reduced by the incorporation O HNCHZCHZOH or coating of these ethoxylated aliphatic tertiary or o HNCH 3 ditertiary amines of the above formula. These tertary and ditertiary amines are effective without discoloring the yarn.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Some of the preferred embodiments of this invention are set forth in the following examples. The method of testing for ozone fading was similar to the AATCC 129-1968set forth on page 334/15 of the Journal of American Association of Textile Chemists and Colorist, Jul. 30, 1969, Vol. 1, No. 16 in an article entitled, A New Test Method For Ozone Fading at High Humidity, by Victor S. Slavin.

EXAMPLE I The following are examples of the subject additives and their behavior on being added to nylon polymer chips, spun into yam, dyed, and exposed to ozone.

The polymer was polycaprolactam of about 20,000-

number average molecular weight, about 60 formic acid reactive viscosity, (FAV), about 50 amine ends per grams polymer and 50 carboxyl ends per 10 grams polymer, which contained about 10 ppm of manganese as manganese chloride, about 25 ppm of phosphorous as hypophosphorous acid, and about 0.13% TiO as a delustrant. The additives were added to the nylon polymer immediately before spinning.

The polymer was spun into 16 filaments having a total denier of about 230, at a spinning temperature of about 260 to 265C. The yarn was drawn at a ratio of 3.2.

The yarn was knitted into sleeves and dyed with Olive I dye which consists of 0.069 percent on weight of fabric (O.W.F.) of CI. Disperse Blue 3, such as Celliton Blue FFRN, (1-methylamino-4-hydroxyethylaminoanthraquinone), 0.0807 percent (O.W.F.) Celliton Pink RF, (CI Disperse Red 4) and 0.465 percent (O.W.F.) Celliton Yellow GA (CI Disperse Yellow 3). The Disperse Blue 3 is especially sensitive to ozone fumes.

The sleeves were scoured before dyeing with a solution of 0.5 percent (O.W.F.) Triton X-lOO, a nonionic alkaryl polyether alcohol by Rohm and Haas and 2.0 percent (O.W.F.) trisodium phosphate at 160F. for about 30 miniutes.

The sleeves were dyed with the above dyes and with 0.5 percent (O.W.F.) Triton X-100, and 2.0 percent (O.W.F.) trisodium phosphate, at 205F. for 1 hour. The sleeves were dyed individually so that the same amount of dye would be picked up by each sleeve.

The sleeves were then subjected to an ozone atmosphere of about 80 pphm (parts per hundred million) ozone at a temperature of 104F., at a relative humidity of at least 95 percent, for 3 cycles. A cycle is that amount of exposure which occurs when a nylon control fabric dyed Olive 1 shows a specified color change as measured by a colorimeter.

This method is similar to, but not identical with, proposed AATCC Test Method 129-1968.

The results of the sleeves being exposed to three cycles of ozone are as follows:

Ethomeen C12 is an ethoxylated cocoa amine, with two moles of ethylene oxide per mole of amine.

Ethomeen T12 is an ethoxylated tallow amine with two moles of ethylene oxide per mole of amine.

Ethomeen 18/12 is an ethoxylated stearyl amine with two moles of ethylene oxide per mole of amine.

Ethoduomeen TD13 is a polyethoxylated diamine where the nitrogens are separated by three or four methylene groups, a tallow radical is attached to one nitrogen, with three moles of ethylene oxide per mole of diamine. V

A E is a measure of the change of color, a smaller A E being less fading.

COLOR DIFFERENCE (A E) A E= V (AL) (Aa) (Ab) L, a and b are readings on the Hunterlab Color Difference Meter. L is a -0 reading of white to black measurement. a measures redness when and gray when zero and green when minus. b measures yellow when gray when zero and blue when minus.

The l-lunterlab Color Difference Meter measures color as seen in average daylight, in a manner similar to the way in which the human eye responds to the stimulus of color. Experimentation has shown that the eye can match any color with a combination of three primary colored lights, and therefore, that any color can be specified by a three dimensional identification. The Color Difference Meter measures the light reflected by a specimen through filters that correspond to the three primary" lights. The measurements made, therefore, correspond to the way the average human eye responds to light, as these responses are set forth in the CIE Standard Observer. The Standard Observer is a table of values derived from experiments with human observers, and recommended for use in 1931 by the International Commission on Illumination (ICI).

HEIXVAMPLEII.

One thousand 1,000) grams of polycaprolactam of 60 FAV, and containing about 90 equivalents of sulfonate as sodium sulfoisophthalic acid having about 80 carboxyls and 20 amines per 10? grams of polymer were blended with 10 grams of Ethomeen T12. This polycarbonamide has a large number of sulfonate groups along the polymer chain. This blend was spun into yarn at a temperature of 280C, plied and drawn at 3.2 draw ratio into a filament 2,100 total denier yarn. The filaments had a Y-cross section with a 3.2 modification ratio.

This yarn and a yarn made in the same manner, but without blending in any additive, were both knitted into sleeves. These sleeves were heat set by steam treating in an autoclave at 230F. for 5 minutes followed by 3 10-minute cycles of steam treatment at 260F.

The sleeves were dyed to a moss green in a dye bath described below containing Astrazon Blue 3R1. This dye is known to be sensitive to ozone. Percents are on weight of fabric:

03 percent Sevron Yellow 8GMF (duPont); (Cl Basic Yellow-53) 0.25 percent Astrazon Blue 3RL (Verona); (Cl Basic Blue 47) 2 percent Hipochem PND-l 1, amine salt of alcohol ester by Highpoint Chemical Company 1 percent Hipochem CDL-60 -nonionic surfactant by Highpoint Chemical Company, (chemical structure not available); enough monosodium and/or disodium phosphate to adjust pH to 7 i 0.2.

w The sleeves were then exposed to 9 cycles of ozone,

as described in Eample l. The results are shown in the following table:

3 cycle 6 cycle 9 cycle Yarn AL AE AL AE AL AE Control nylon 3 5 9 14 15 21 1% Ethomeen T12 2 2 4 6 7 1O EXAMPLE 111 Other blends were made and processed as in Example II. The results of ozone testing are tabulated below:

Additive to Polymer 3 cycle AB 9 cycle AE None (Control) 5 21 1% Ethomeen 18/12 2 l EXAMPLE IV Cationic dyeable yarn like that in Example I] of 2,100 total drawn denier, 140 filaments, Ycross section, of 3.2 modification ratio, was treated with an aqueous spin finish containing sufficient Ethomeen T12 so that 1 percent of it was put on the fiber. The drawn yarn was treated and tested as in Example II. The results of ozone testing are as follows:

3 cycle 6 cycle 9 cycle AL AE AL AE AL AE Control 8 15 22 19 28 1% Ethomeen T12 (OWF) 2.5 4.5 7 10 EXAMPLE V Cationic dyeable yarn was spun and drawn as in the control of Example IV, but a portion of the yarn was treated with an overfinish consisting of a 20 percent solution of Ethomeen 18/12 in ethanol. About 5 percent pickup of the overfinish (on weight of fiber, OWF) was obtained. Thus, about 1 percent (OWF) of Ethomeen resulted. The yarns were treated as in Example II and submitted to ozone testing. The results are as follows:

3 cycles 6 cycles 9 cycles AL AE AL AE AL AE Control 5 8 15 22 19 28 With Overfinish 0.5 1 1.5 2 1.5 3

' EXAMPLE VI These ethoxylated aliphatic amines may also be applied to textiles or carpet as a minor component in a dye bath.

A sleeve similar to the control sleeve of Example 11 was dyed in a dyebath containing the dyes of Example II. A second portion of the same sleeve was dyed similarly but with the addition of 1 percent Ethomeen T12 (on the weight of Fiber) to the dye bath. The dyed sleeves were exposed to ozone. The results are below:

3 cycles 6 cycles 9 cycles AL AE AL AE AL AE Control 3.5 5 9 l3 l3 19 With 1% Ethomeen T12 in Dye Bath 0.5 l l 2.5 3 5 EXAMPLE Vll Cationic dyeable yarn like that in Example IV except having about 81 equivalents of sulfonic groups, per 10 g ims of polymer, 46 FAV, 89 carboxyl ends, and

' and processed as in Example llexcept the dye was Disamine ends per 10 grams of polymer was spun as in Example ll without Ethomeen compound added, drawn at about 3.2 draw ratio to obtain yarn of same denier, modification ratio, and filament count as Example II, and heat set as in Example 11. The sleeves were dyed moss green in a dyebath composition as in Example 11.

The spin finish contained Ethomeen T12 to achieve the percent on weight of yarn given in the table below.

The sleeves were then exposed to 9 cycles of ozone, as described in Example 1. The results are shown in the table below:

yarn as in Example VII, a 5,000 No. commericial plant trial was conducted. About 1.1 percent Ethomeen T12 was applied on the weight of yarn. The yarn was drawn 2.9 times and chopped to 7 inch length, carded and spun into staple yarn with a 2 cotton count. The yarn was woven into sleeves, and heat set as in Example 11. Following are the results of ozone exposure after up to nine cycles as described in Example I. Dyeing was as in Example VII.

3 cycles 6 cycles 9 cycles AL AE AL AE AL AE Control 5 7 8 12 12 17 Sample 05 0.7 1 1.5 1.5 3

EXAMPLE IX A second plant trial duplicating Example VIII was carried out but only 0.6 percent on weight of yarn of Ethomeen T12 was applied with the following results:

3 cycles 6 cycles 9 cycles AL AE AL AE AL AE Control 5 7 10 14 15 21 Sample I 2 4 6 7 10 EXAMPLE X A bright, sebacic acid terminated polycaprolactam with FAV, about 63 carboxyl ends and 15 amine ends per 10 equivalents of polymer were commercially spun and drawn at a ratio of 3.05 to a 6,400 denier, filament Y-cross section, 3.2 modification ratio yarn. This nylon has a preponderance of terminal carboxyl groups. The yarn was coated with a spin finish to provide 0.55 percent on weight of yarn of Ethomeen T12;

perse Olive II from a dyebath as follows (percent on weight of fabric):

0.082 percent Latyl Cerise Y;

0.44 percent Celliton Yellow GA;

0.143 percent Celanthrene Blue CR;

2 percent trisodium phosphate;

0.5 percent Triton X-l00 (ethoxylated nonyl phenol) Testing for ozone fading as in Example I gave the following results:

3 cycles 6 cycles 9 cycles AL AE AL E AL AE Control 1.5 3 4 6 5 9 Sample 0.5 1 0.5 1.5 0.5 2.5

EXAMPLE X(A) The same undrawn yarn as in Example X was drawn Dyed with formulation as in Example X above, results were as follows:

3 cycles AL 6 cycles 9 cycles E AL A AL AE Control 1 Sample 0 LIILII EXAMPLE XI Using polymer as in Example VII, chips were blended with 1 percent by weight of Ethomeen T12 and Ethoduomeen TD-l3 and processed and tested as in Example II. Results were as follows:

3 cycles 6 cycles 9 cycles AL AE AL AE AL AE Control 5 8 ll l6 19 26 Sample with T12 1 2 6 7 ll 14 Sample with TD-13 2 3 4 6 9 l3 EXAMPLE XII Using yarn of the same characteristics as in Example VII, a spin finish of Ethom een T-l2 was applied to yarn to the weight on yarn shown below. Processing and testing was as in Example VIII, with the following results:

3 cycles 6 cycles 9 cycles AL A AL AB Control 7 10 15 22 21 29 0.21% T12 5 8 l0 l6 16 24 0.41% do. 2 3.5 6 9 ll 16 1.5 3 4 7 9 13 -Continued 3 cycles 6 cycles 9 cycles AL AE AL AE AL AE 0.9% do. 0.5 1.5 4 6 8 11 1.08% do. 0.5 l 1.5 3 5 7 EXAMPLE XIII A spin finish to give 0.7 percent weight on yarn of Ethomeen T12 to the yarn prepared from polymer as in Example X and spun, drawn, and heat-set as in Example II to provide the following results, from testing as in Example I and dyeing as in Examples X and X(A).

3 cycles 6 cycles 9 cycles Olive I dye AL AE AL AE AL AE Control 5 9 12 19 16 24 Sample 1 2.5 6 9 9 15 Olive II dye Control 1 2 4 6 6 9 Sample 0.5 0.5 0.5 2 2 4 EXAMPLE XIV Repeating Example XIII, but using a light stable, semi-dull polycaprolactam of FAV, 63 carboxyl end groups and 15 amine end groups per 10 equivalents of polymers yielded the following results.

3 cycles 6 cycles 9 cycles Olive I dye AL AE AL AE AL AE Control 7 10 11 19 19 27 Sample 1.5 2.5 6 9 11 16 Olive II dye I Control 0 1 6 8 8 12 Sample 0 0.5 1.5 2 5 3 4 EXAMPLE XV Example VII was repeated using the percent on weight of yarn shown of Ethomeen T12,Eth0duomeen TD-l3 and Ethomeen T-l5. Results were as follows:

3 cycles 6 cycles 9 cycles AL AE AL AE AL AE Control 4 7 16 23 21 30 0.8% T12 1.5 2 5 8 9 14 0.8% TD-13 0.5 1.5 5 7 8 13 1.0%T-15* 1.5 2 4 6 8 12 Ethomeen T-l5 is an elhoxylaled tallow amine with 5 moles of ethylene oxide per mole of amine.

EXAMPLE XVI The procedure of Example VIII was repeated on a small scale, using a similar polymer but containing about equivalents of sulfonic groups per 10 grams of polymer. Conventional spin finish was used, but various amounts of Ethomeen T12 were added in the dyebath rather than in the spin finish. Percent shown is on weight of fabric. Results were as follows:

3 cycles 6 cycles 9 cycles AL AE L AE AL AE Control 4 6 1 l6 17 24 0.1% T12 3 5 14 15 21 0.5% T12 l 2 6 8 9 12 1.0% T12 0.5 l 2 4 6 8 EXAMPLE XVII The procedure of Example VIII was repeated on a smaller scale using a cationic dyeable nylon 6,6 staple (duPont T3 67). Conventional spin finish was used, but various amounts of Ethomeen T-l2 were added in the dyebath rather than in the spin finish. Percent shown is on weight of fabric. Results were as follows:

3 cycles 6 cycles 9 cycles AL AE AL AE AL AE Control 2 4 3 5 7 0.1% T12 1.5 2.5 3 5 5 7 0.5% T12 0.5 l 2 3 3 4 0.5 l 1 2 2 3 EXAMPLE XVIII AE AL Control 7.3 4.8 2% Ethomeen Tl2 4.6 2.6 3% Ethomeen T12 4.6 2.4

It can be seen that the additive is relatively less effective when added prior to polymerization.

EXAMPLE XIX Polycaprolactam staple yarn as in Example VII was spun and processed as in Example VII but with various aqueous spin finishes. All finishes were 20 percent solids" and 80 percent water. Of the solids," 40 percent was the additive listed below.

The yarns were drawn, knitted into sleeves, autoclaved. dyed and exposed to ozone. The results of ozone exposure were as follows:

Finish AE after Additive Pickup 3 cycles None, control 12.2 N.N-bis(2-hydroxycthyl)-l-aminol0.2 8.0 lli-phenyloctad ecane N.N-bis(Z-hydroxyethyU-Z-amino 10.0 7.5 octadecane EXAMPLE XX Polymer made from caprolactam, having a formic acid relative viscosity of 46, about 81 sulfonic groups from sodium sulfoisophthalate.about 90 carboxyls and about 25 amine ends per million grams of polymer, was spun into yarn. The yarn, coated with a commercially aqueous spin finish was drawn at a draw ratio of 2.9. The yarn had a Y cross-section with a 3.2 modification ratio and each filament had a denier of 15.

The yarn was chopped into 7 inch lengths, carded and spun into staple yarn having a cotton count of 2. The yarn was knitted into sleeves, and heat set by steam treating in an autoclave at 230F. for 5 minutes followed by 3 10-minute cycles of steam treatment at 260F.

The sleeves were dyed to a moss green in a dye bath composed as follows:

0.3 percent Sevron Yellow 8GMF (DuPont) 0.25 percent Astrazon Blue 3RL (Verona) 2.0 percent Hipochem PND-ll 1.0 percent Hipochem CDL- and monosodium and/or disodium phosphate to adjust the pH to 7.0 i 0.2

The sleeve was cut into sections about 5 inches long and each section was weighed. The sleeves were then dipped in the ethanol solutions shown below for 20 minutes. The sleeves were then removed from the solutions, dried and reweighed. The amount of material coated on the sleeves from each solution was based on the difference in weight between the coated and the uncoated sleeves, compared to the control.

The sleeves were then exposed to 3 cycles of ozone in an atmosphere of about parts per hundred million of ozone at a temperature of a 104F., at a relative humidity of at least percent. A cycle is that exposure which is completed when the internal nylon standard, dyed olive I, has faded sufficiently to give a A E of 2.8. The measurement A E is discussed under Description of Preferred Embodiments."

The solutions, the amount of coating and the results of ozone exposure are listed below:

% Pickup A5 (a) Control-200 ml. of ethanol 0 13.4 (b) 1 gram of N.N-bis(2-hydroxyethyl)-lamino-IS-phenyl stearylamine in 200 ml. ethanol [.3 2.0

(c) 1 gram of N.N-bis(2-hydroxyethyl)-2- amino octadecane in 200 ml. ethanol L! 1.5 (d) 1 gram N,N-bis (2hydroxyethyl)-2'- ethyl hexylamine in 200 ml. ethanol 0.8 2.3 (e) 1 gram N,N.N'-tris(2-hydroxyethyl)-2- amino octadecane in 200 ml. ethanol 1.1 1.7 (f) I gram bis ethoxylated Primene 81 R* (2 moles ethylene oxide per mole of amine) in 200 ml. ethanol 0.9 2.2

*Irimene 81R is principally I'CuHgnNHz to t-C HsuNH manufactured by Rohm 8L Haas.

RCH N(CH CH H (CH CH O) H or mixtures of them where R is straight chain alkyl, branched chain alkyl or aralkyl containing 7 to 24 carbon atoms, said R can contain up to two oxygen atoms as ester or ether linkages, R is a straight chain alkylene radical having 2 to 10 carbon atoms, and x, y and z are each at least 1 and x, y and 2 total not more than 15, so that from about 0.1 to about 8 percent on weight of fiber of said compound remains on said fibers to reduce the fading of dyed polycarbonamide fabrics caused by ozone.

2. The method of claim 1 wherein the amine compound is present in amount between 0.1 and 5 percent by weight of fiber.

3. In a method for dyeing polycarbonamide fibers with antraquinone dyes the improvement comprising coating said fiber with a substance consisting essentially of a compound selected from the group consisting of tertiary amines and ditertiary amines of theformula (CH CH O) H A. RCH N (CH CH O YH (CH2CH2O)XH B. R' N CH 0 2 H 0)yH RCa MGH CH M H or mixtures of them where R is straight chain alkyl, bracnched chain alkyl or aralkyl containing 7 to 24 carbon atoms, said R can contain up to two oxygen atoms as ester or ether linkages, R is a straight chain alkylene radical having 2 to 10 carbon atoms, and x, y and z are each 1 a P so that from about 0.1 to about 8 percent on weight of fiber of said compound remains on said fibers to reduce the fading of dyed polycarbonamide fabrics 9.223%1 y Ozone- 4. The method of claim 3 wherein the polycarbonamis eisrg yc p 5. The method of claim 3 wherein the polycarbonamide is polyhexamethylenediamine adipate.

6. The method of claim 1 wherein said coating is applie rim. to dy ai b 8. The method of claim 1 wherein said coating is applied subsequent to dyeing said fiber.

4 9. The method of claim 1 wherein said anthraquinone dyes aredisperse dyes.

10. The method of claim 1 wherein said anthraquinone dyes are basic dyes.

I I =i 

1. IN A METHOD FOR DYEING POLYCARBONAMIDE FIBERS SAID POLYCARBONAMIDE HAVING PREPONDERACE OF TERMINAL CARBOXYL ROUPS OR IS A POLYMER CHAIN WITH A LARGE NNUMBER OF SULFONATE GROUPS ALONG THE POLMER CHAIN WITH ANTHRAQUINONE DYES THE IMPROVEMENT COMPRISING COATING SAID FIBER WITH A SUBSTANCE CONSISTING ESSENTIALLY OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF TERTIARY AMINES AND DITERTIARY AMINES OF THE FORMULA
 2. The method of claim 1 wherein the amine compound is present in amount between 0.1 and 5 percent by weight of fiber.
 3. In a method for dyeing polycarbonamide fibers with antraquinone dyes the improvement comprising coating said fiber with a substance consisting essentially of a compound selected from the group consisting of tertiary amines and ditertiary amines of the formula
 4. The method of claim 3 wherein the polycarbonamide is polycaprolactam.
 5. The method of claim 3 wherein the polycarbonamide is polyhexamethylenediamine adipate.
 6. The method of claim 1 wherein said coating is applied prior to dyeing said fiber.
 7. The method of claim 1 wherein said coating is applied concurrently to dyeing said fiber by adding said compound to a dyebath.
 8. The method of claim 1 wherein said coating is applied subsequent to dyeing said fiber.
 9. The method of claim 1 wherein said anthraquinone dyes are disperse dyes.
 10. The method of claim 1 wherein said anthraquinone dyes are basic dyes. 